CN104804385B - A kind of manufacturing method of biodegradable plastics master batch and application - Google Patents
A kind of manufacturing method of biodegradable plastics master batch and application Download PDFInfo
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- CN104804385B CN104804385B CN201410029614.2A CN201410029614A CN104804385B CN 104804385 B CN104804385 B CN 104804385B CN 201410029614 A CN201410029614 A CN 201410029614A CN 104804385 B CN104804385 B CN 104804385B
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Abstract
The invention discloses a kind of production methods of biodegradable plastics master batch, include mainly following component：Modify compatilizer 20% 65%, biocatalyst 20% 35%, nutritional agents 20% 35%, catalyst 10% 15%, interfacial agent 0.5% 6%, glycerine 1% 3%；First by catalyzer temperature-elevating to 200 DEG C~300 DEG C high temperature dehydrations, and 1~2 hour dry, then it is ground to more than 5000 mesh；Later by nutritional agents, interfacial agent, glycerine is added to Catalyst Adsorption, 35 DEG C~50 DEG C of temperature, and using homogenizer stirring at low speed 3~5 minutes, until after all liq is fully absorbed, the flowing shape of powder is presented；Compatilizer, biocatalyst and the catalyst that is stirred will be modified and be directly placed into kneading machining；Biodegradable agglomerate is made, the sum of said components of master batch are not more than 100%.
Description
Technical field：
The present invention relates to biodegradable plastic field more particularly to it is a kind of can fast decoupled in the natural environment modeling
The method for making of material and the plastics.
Background technology：
With white pollution, getting worse, solve the problems, such as plastics a century is not changed, biodegradation technique come into being but
Even to this day it, can not still implement solution and pollution still remains, has four with regard to its reason：1, Partial digestion is broken bad：Plastics add
Starch, starch degradation, plastics do not decompose, only reach Partial digestion, 2, storage and be restricted using it：Photolysis agent, heat are bad
Though solution agent, can reach fragmentation fragmentate but be unfavorable for store and transport and use during quality physical property decline, service life
It is limited；3, the recovery system of plastics is destroyed：Plastics addition and the agent of photo-thermal solution can not recycle and can not classify, lead to original plastics
Recovery system, because being added accidentally, due to destroy physical property and can not use, 4, it is too expensive：Raw matter plastics such as PLA, PCL, PHA unit price
It is too high, it can not popularize, and all plastic properties can not be replaced, in addition recycling is even more to destroy physical property.
In view of this, the present inventor through concentrating on studies, add in the plastic a kind of preparation, so that plastics using completing
It afterwards, can the destruction of fast decoupled, reduction to environment in the natural environment.This invention is above-listed to solve the problems, such as, with reference to nature
Rule, using large natural environment bacterial decomposition mode, because burying in rubbish, oxygen is seldom, and aerobic breakdown is difficult to carry out, so
Anaerobic bacteria decomposition plastics are easier to carry out, but the time is longer, and this invention is the condition for providing anaerobic bacteria and being easy hyperplasia breeding,
Biocatalyst is added in plastics, the nutritional agents of bacterium, catalyst, interfacial agent etc. is conducive to the condition of anaerobic bacteria hyperplasia, and makes
Accelerated decomposition, hydrolyze, acidification acetifies, is ultimately breaks down into CO2, CH4, and this invention is after adding above-listed ingredient with plastics, in
Make finished product after processing, without a large amount of anaerobic bacterias, so storing, use, recycling processing is all non-degradable, until being dropped or
Just can be decomposed by the Nature anaerobic bacteria after burial, in order to reach the requirement of processing and facility and economy, he is made concentration by us
Master batch, it is rear easy to use, while many plastics are can be applied to, as PE/PP/EVA/TPE/NYLON/PET all can be used.
Invention content：
This invention be to provide a kind of newest anaerobic bacteria degradation, by anaerobic bacteria accelerated factor, make degradation concentration master batch,
It can be applied to plastics accelerated degradation while having that degradable, storage is unrestricted, does not destroy recovery system, low cost is succinct high
A kind of preparation method of effect.
To achieve the goals above, the present invention uses following technical scheme：
A kind of production method of biodegradable plastics master batch includes mainly following component：
The compatilizer 20%-65% of modification, biocatalyst 20%-35%, nutritional agents 20%-35%, catalyst 10%-
15%, interfacial agent, 0.5%-6%, glycerine 1%-3%；
First by catalyzer temperature-elevating to 200 DEG C~300 DEG C high temperature dehydrations, and 1~2hrs is dried, then ground to 5000 mesh
More than, make its oil absorbing effect up to 5 times, 0.3 or less apparent specific gravity (gd)；
First by the nutritional agents of liquid, interfacial agent, processing oil is added to the oxide adsorbent of powder, temperature 35 DEG C~50
DEG C suction effect is best, with homogenizer, stirring low speed 3~5 minutes, until all liq is standby fully absorb after, powder is presented
Flowing shape；
The compatilizer of modification and biocatalyst and the catalyst being stirred are directly placed into kneading machining, 100 DEG C of temperature
~150 DEG C, pressurization kneading, 15~20min of kneading makes it fully mix；
Plastics and biological decomposition master batch are fully mixed via extrusion, keeper, blown film, blow bottle, project at required finished product its
Adding proportion 0.5~50%.
The compatilizer of modification can be LLDPE-MA, LLDPE-AA, PE-MA, PE-GMA, EVA-MA, EVA-AA, PO-AA-
MA, SEBS-MA, SEBS-GMA or all kinds of MA, AA, GMA's connects branch modified plastics.
Biocatalyst be containing organic lipid, have biological decomposition material, such as aliphatic acid etc, lactic acid, hyaluronic acid
Etc, phosphoric, lauric acid etc, etc. biodegradable fat it is organic etc
Nutritional agents be polysaccharides, such as candy honey or clarified butter essence, sugarcane candy, be anaerobic bacteria hobby organic carbohydrate.
Catalyst：Alkali metal oxide, such as calcium oxide, magnesia, aluminium oxide, silica containing the crystallization water or without crystallization
The anhydrous crystal oxide 60~5% or the natural oxide of shellfish, crab shell class through high temperature dehydration of water or magnesium sulfate
Interfacial agent be one end lipophilic group other end be hydrophilic group, such as silanes coupling agent, metatitanic acid fat
Lipoid coupling, zirconic acid lipid, or sour amides, or metallic soap of stearic acid, fatty acid amide, its can make nutritional agents and compatibility
Agent is combined with each other 5%-50%
Processing oil can make vegetable oil, glycerine, one fat of glycerine, dialycerides, triglyceride, citric acid tri butyl ester oil, big
Soya-bean oil, olive oil.
A kind of biodegradable plastics master batch be applied to agricultural film master batch production method,
Including following components：
3 kilograms of calcium oxide for being added 30 kilograms of glycerine are taken first, are stirred evenly, and 30 DEG C~40 DEG C x300RPM stir three points
Clock will mix good glycerine and CaO and LLDPE-MA, and 110 DEG C of mix temperature of pressurizeing kneads 15min to 150 DEG C；Master batch is made.
A kind of biodegradable plastics master batch is applied to the master batch production method of industrial bag：
Including following components：
3 kilograms of glycerine is added to 20 kilograms of magnesia, is stirred evenly, 30 DEG C~40 DEG C x 300RPM stir three minutes,
Good glycerine will be mixed and MgO and PE-MA, other mixtures are put into kneading machine, 110 DEG C of mix temperature of pressurizeing kneads 15min
To 150 DEG C；Master batch is made.
A kind of biodegradable plastics master batch is applied to the master batch production method of PP packaging plate bags：
Including following components：
It by 3 kilograms of magnesia for being added 25 kilograms of glycerine, stirs evenly, 30 DEG C~40 DEG C x 300RPM are stirred three minutes；
Good glycerine and MgO and POE-MA will be mixed and other mixtures are put into kneading machine, 110 DEG C of mix temperature of pressurizeing, 15min,
Material temperature is given birth to 150 DEG C at this time, pours into conveyer mechanism extruder, and 110 DEG C of mix temperature of pressurizeing kneads 15min to 150 DEG C；It is made
Master batch.
Decomposition catalyst in plastics notes point, by catalyst hydrolysis acidification so that hydrophobic frosting is formed via anaerobic bacteria
Hydrophilic surface layer, and anaerobic bacteria can decompose its peculiar enzyme, attract bacterium bunching effect, in addition there is the nutrition of bacterium in plastics
Agent so that anaerobism is bred hyperplasia and accelerated, and plastics are swollen tough, is catalyzed the plastic construction that accelerates the failure：Because catalyst hydrolyzes in plastics, acid
Change, form alkali metal oxidising agent in acetate, and plastics, form acid-base neutralization reaction, and destroy molecular structure so that outside water
Layer enters plastics inner so that fine and close plastic expansion while anaerobic bacteria gets enter into deep layer plastics, accelerated decomposition hydrolysis, acid
Change eventually forms low molecular weight organic fatty acid compound, finally reaches degradable purpose.
Specific implementation mode
According to embodiment, the present invention is described in further detail below：
Embodiment one：
A kind of biodegradable plastics master batch is applied to the biological decomposition master batch making of agricultural film：
Compatible modification agent：MI=5~25 LLDPE-MA
Biocatalyst：Between poly- friendship fat MW=10000~100000 of low molecular weight lactic acid, molecular weight is too high, catalyst：
2 μm of CaO average grain diameters
Chitin：It is powdered, it is all filtered through airflow milling 325mesh
Interfacial agent：Stearmide is powdered
Glycerine：Higher boiling
Method A：
3 kilograms of calcium oxide for being added 30 kilograms of glycerine, stir evenly, and 30 DEG C~40 DEG C x 300RPM are stirred three minutes；It will
It mixes good glycerine and CaO and LLDPE-MA, other mixtures is put into kneading machine, 110 DEG C of mix temperature of pressurizeing, 15min, this
When material temperature give birth to 150 DEG C, pour into conveyer mechanism extruder, extruder temperature, be set as 120 DEG C/120 DEG C/125 DEG C/130 DEG C/
135 DEG C of rotating speed 100rpm dry type pelletizings of Die, cool down through reciprocating sieve, and with aluminum foil sack, packaging prevents moisture content from immersing
Method B：
3 kilograms of calcium oxide for being added 30 kilograms of glycerine, stir evenly, and 40 DEG C of x 300RPM are stirred three minutes；It will mix
Glycerine and CaO and LLDPE-MA, other mixtures, which are added blenders and uniformly mix, to be stirred 3 minutes；Good mixture will be mixed
It is fed in twin shaft extruder using twin shaft feeder, processing conditions extruder temperature is set as 120 DEG C/130 DEG C/135 DEG C/130
DEG C/115 DEG C of rotating speed 300rpm dry type pelletizings of Die, it is cooled down through reciprocating sieve, with aluminum foil sack, packaging prevents moisture content from immersing.
Embodiment 2：
A kind of biodegradable plastics master batch is applied to the decomposition master batch processing technology example of shopping bag plastic bag：
90 DEG C of x 1hrs of processing temperature baking material temperature
165 DEG C/170 DEG C/175 DEG C/180 DEG C~185 DEG C/die/180 DEG C~185 DEG C of processing temperature
/ 180 DEG C~185 DEG C, mesh：60x2 is sieved.
Embodiment 3：
A kind of biodegradable plastics master batch is applied to the decomposition master batch processing technology example of industrial bag：
Compatible modification agent：MI=5~25 PE-MA
Biocatalyst：Between low molecular weight adipic acid hexylene glycol fat MW=10000~30000,
Catalyst：2 μm of MgO average grain diameters
Chitin：It is powdered, it is all filtered through airflow milling 325mesh
Interfacial agent：A-172
Glycerine：Higher boiling glycerine
Method A：
By 3 kilograms of magnesia for being added 20 kilograms of glycerine, stirring evenly, 30 DEG C~40 DEG C x 300RPM are stirred three minutes,
Good glycerine will be mixed and MgO and PE-MA, other mixtures are put into kneading machine, 110 DEG C of mix temperature of pressurizeing, 15min, this
When material temperature give birth to 150 DEG C, pour into conveyer mechanism extruder, extruder temperature, be set as 120 DEG C/120 DEG C/125 DEG C/130 DEG C/
135 DEG C of rotating speed 100rpm dry type pelletizings of Die, cool down through reciprocating sieve, and with aluminum foil sack, packaging prevents moisture content from immersing.
Method B：
3 kilograms of magnesia for being added 20 kilograms of glycerine, stir evenly, and 40 DEG C of x 300RPM are stirred three minutes, will be mixed
Glycerine and MgO and PE-MA, other mixtures blenders are added and uniformly mix stirring 3 minutes, good mixture utilization will be mixed
Twin shaft feeder feed twin shaft extruder in, processing conditions extruder temperature, be set as 120 DEG C/130 DEG C/135 DEG C/130 DEG C/
115 DEG C of rotating speed 300rpm dry type pelletizings of Die, cool down through reciprocating sieve, and with aluminum foil sack, packaging prevents moisture content from immersing.
Embodiment 4：
A kind of biodegradable plastics master batch is applied to the decomposition master batch processing technology example of PP packaging plate bags：
Compatible modification agent：POE-MA can use DOW 8400 to be grafted MI=5~10 MA
Biocatalyst：Between low molecular weight adipic acid hexylene glycol fat MW=10000~30000,
Catalyst：2 μm of MgO average grain diameters
Chitin：It is powdered, it is all filtered through airflow milling 325mesh
Interfacial agent：A-172
Glycerine：Higher boiling glycerine
Method A:
It by 3 kilograms of magnesia for being added 25 kilograms of glycerine, stirs evenly, 30 DEG C~40 DEG C x 300RPM are stirred three minutes will
It mixes good glycerine and MgO and POE-MA, other mixtures is put into kneading machine, 110 DEG C of mix temperature of pressurizeing, 15min, at this time
Material temperature is given birth to 150 DEG C, and conveyer mechanism extruder is poured into, and extruder temperature is set as 130 DEG C/140 DEG C/145 DEG C/150 DEG C/Die
155 DEG C of rotating speed 100rpm dry type pelletizings, cool down through reciprocating sieve, and with aluminum foil sack, packaging prevents moisture content from immersing.
Method B：
3 kilograms of magnesia for being added 25 kilograms of glycerine, stir evenly, and 40 DEG C of x 300RPM are stirred three minutes, will be mixed
Glycerine and MgO and POE-MA, other mixtures blenders are added and uniformly mix stirring 3 minutes, it is sharp good mixture will to be mixed
It is fed in twin shaft extruder with twin shaft feeder, processing conditions extruder temperature is set as 130 DEG C/140 DEG C/145 DEG C/150
DEG C/155 DEG C of rotating speed 300rpm dry type pelletizings of Die, it is cooled down through reciprocating sieve, with aluminum foil sack, packaging prevents moisture content from immersing.
PP packaging plates match：
Requirement condition：PP 100cm x 0.3mm X 1000M
PP 366 80KG
Biological decomposition master batch 10kg
TALC master batch PT-80 20kg
180 DEG C/185 DEG C/190 DEG C/205 DEG C/die210 DEG C/220 DEG C mesh 60x2 speed 50m/ of extrusion slab temperatures
min
Scope of application general industry with packaging plate, bury earthing about 1~2 year and decompose completely
Embodiment 5
A kind of biodegradable plastics master batch is applied to the decomposition master batch processing technology example of PP nonwoven fabrics：
Compatible modification agent：POE-MA can use DOW 8400 to be grafted MI=10~20 MA
Biocatalyst：Between low molecular weight adipic acid hexylene glycol fat MW=10000~30000,
Catalyst：1 μm of MgO average grain diameters
Chitin：It is powdered, it is all filtered through airflow milling 325mesh
Interfacial agent：A-172
Acetyl tributyl citrate tri butyl ester：
Step：Method A stirs evenly 3 kilograms of magnesia for being added 20 kilograms of acetyl tributyl citrate tri butyl ester, 30 DEG C~40
DEG C x 300RPM is stirred three minutes, will mix good acetyl tributyl citrate tri butyl ester and MgO and POE-MA, other mixtures, which are put into, to be pinched
In machine, pressurize 110 DEG C, 15min of mix temperature, at this time material temperature give birth to 150 DEG C, pour into conveyer mechanism extruder, extruder temperature
Degree, is set as 120 DEG C/120 DEG C/125 DEG C/130 DEG C/Die, 135 DEG C of rotating speed 100rpm dry type pelletizings, is cooled down through reciprocating sieve, uses
Aluminum foil sack, packaging prevent moisture content from immersing
Step：20 kilograms of magnesia is added in 3 kilograms of acetyl tributyl citrate tri butyl esters by method B, is stirred evenly, 40 DEG C of x
300RPM is stirred three minutes
Good acetyl tributyl citrate tri butyl ester and MgO and PE-MA will be mixed and other mixtures are added blender and uniformly mix
Stirring 3 minutes will mix good mixture and be fed in twin shaft extruder using twin shaft feeder, processing conditions extruder temperature,
It is set as 120 DEG C/130 DEG C/135 DEG C/130 DEG C/Die, 115 DEG C of rotating speed 300rpm dry type pelletizings, is cooled down through reciprocating sieve, use aluminium foil
Packaging bag, packaging prevent moisture content from immersing PP nonwoven fabric material mixture ratios：
PP MI=100 90KG
Biological decomposition master batch MP-10 10kg
180 DEG C/185 DEG C/190 DEG C/205 DEG C/die210 DEG C/220 DEG C of extrusion nonwoven fabric temperature
Scope of application general industry with packaging plate, bury earthing about 1~2 year and decompose completely.
Embodiment 6
A kind of biodegradable plastics master batch is applied to the decomposition master batch processing technology example of PET FIBER：
Compatible modification agent：POE-MA can use DOW 8400 to be grafted MI=10~20 MA
Biocatalyst：Between low molecular weight adipic acid hexylene glycol fat MW=10000~30000,
Catalyst：1 μm of MgO average grain diameters
Chitin：It is powdered, it is all filtered through airflow milling 325mesh
Interfacial agent：A-172
Acetyl tributyl citrate tri butyl ester：
Method A：
By 3 kilograms of magnesia for being added 20 kilograms of acetyl tributyl citrate tri butyl ester, stir evenly, 30 DEG C~40 DEG C x
300RPM is stirred three minutes, will mix good acetyl tributyl citrate tri butyl ester and MgO and SEBS-GMA, other mixtures, which are put into, to be pinched
In machine, pressurize 150 DEG C, 15min of mix temperature, at this time material temperature give birth to 150 DEG C, pour into conveyer mechanism extruder, extruder temperature
Degree, is set as 150 DEG C/160 DEG C/175 DEG C/170 DEG C/Die, 185 DEG C of rotating speed 100rpm dry type pelletizings, is cooled down through reciprocating sieve, uses
Aluminum foil sack, packaging prevent moisture content from immersing.
Method B：
3 kilograms of acetyl tributyl citrate tri butyl esters are added to 20 kilograms of magnesia, are stirred evenly, 40 DEG C of x300RPM stirrings three
Minute, good acetyl tributyl citrate tri butyl ester and MgO and SEBS-GMA will be mixed, other mixtures are added uniform mix of blender and stir
It mixes 3 minutes, good mixture will be mixed and fed in twin shaft extruder using twin shaft feeder, processing conditions extruder temperature, if
It is set to 150 DEG C/160 DEG C/175 DEG C/170 DEG C/Die, 185 DEG C of rotating speed 300rpm dry type pelletizings, is cooled down through reciprocating sieve, use Aluminium Foil Package
Pack, packaging prevent moisture content from immersing.
PET reels off raw silk from cocoons material mixture ratio：
PET 90KG
Biological decomposition master batch MTE-10 10kg
230 DEG C/235 DEG C/240 DEG C/245 DEG C/die250 DEG C/260 DEG C of extrusion nonwoven fabric temperature
Scope of application general industry is reeled off raw silk from cocoons with PET, is buried earthing and is decomposed completely for about 1~2 year.
Claims (7)
1. a kind of production method of biodegradable plastics master batch includes mainly following component：
Modify compatilizer 20%-65%, biocatalyst 20%-35%, nutritional agents 20%-35%, catalyst 10%-15%, boundary
Face activating agent 0.5%-6%, glycerine 1%-3%；
Wherein biocatalyst is biodegradable organosilane ester；The organosilane ester is selected from fatty acid, lactic acid class, alditol
The ester of acids, phosphoric acid class, sodium laurate；Nutritional agents is polysaccharide body, is molasses, clarified butter essence；
First by catalyzer temperature-elevating to 200 DEG C~300 DEG C high temperature dehydrations, and 1~2 hour dry, then it is ground to 5000 mesh with
On, so that its oil absorbing effect is reached 5 times, 0.3 or less apparent specific gravity (gd)；
Later by nutritional agents, interfacial agent, glycerine is added to Catalyst Adsorption, and 35 DEG C~50 DEG C of temperature uses high-speed stirred
The flowing shape of powder is presented until after all liq is fully absorbed in machine stirring at low speed 3~5 minutes；It will modification compatilizer, biology
Catalyst and the catalyst being stirred are directly placed into kneading machining, 100 DEG C~150 DEG C of temperature, and pressurization is mediated, and kneading 15~
20min makes it be sufficiently mixed；Biodegradable agglomerate is made, the sum of said components of master batch are not more than 100%.
2. a kind of production method of biodegradable plastics master batch according to claim 1, it is characterised in that：It modifies compatible
Agent is the graft modification plastics of all kinds of MA, AA, GMA.
3. a kind of production method of biodegradable plastics master batch according to claim 1, it is characterised in that：Described urges
Agent is alkali metal oxide, and the alkali metal oxide is selected from calcium oxide, magnesia.
4. a kind of production method of biodegradable plastics master batch according to claim 1, it is characterised in that：The boundary
Face activating agent one end is lipophilic group, and the other end is hydrophilic group, selected from silane coupling agent, zirconate coupling agent, stearic acid metal
Soap, fatty acid amide.
5. a kind of production method of biodegradable plastics master batch applied to agricultural film：
Including following components：
It takes 3kg glycerine that 30kg calcium oxide is added first, stirs evenly, 30 DEG C~40 DEG C × 300RPM is stirred three minutes, will be mixed
Good glycerine and CaO, LLDPE-MA and other components are put into kneader, and pressurize 110 DEG C of mixing temperature, mediates 15min extremely
150℃；Master batch is made, the sum of said components of master batch are not more than 100%.
6. a kind of production method of biodegradable plastics master batch applied to industrial bag：
Including following components：
20kg magnesia is added in 3kg glycerine, is stirred evenly, 30 DEG C~40 DEG C × 300RPM stirs three minutes, by what is mixed
Glycerine and MgO, PE-MA and other components are put into kneader, and pressurize 110 DEG C of mixing temperature, kneads 15min to 150 DEG C；System
Master batch is obtained, the sum of said components of master batch are not more than 100%.
7. a kind of production method of biodegradable plastics master batch applied to PP packaging plate bags：
Including following components：
25kg magnesia is added in 3kg glycerine, is stirred evenly, 30 DEG C~40 DEG C × 300RPM is stirred three minutes；By what is mixed
Glycerine and MgO, POE-MA and other mixtures are put into kneader, and pressurize 110 DEG C, 15min of mixing temperature, at this time material temperature liter
To 150 DEG C, conveyer is poured into extruder, pressurize 110 DEG C of mixing temperature, mediates 15min to 150 DEG C；Master batch is made, master batch
The sum of said components are not more than 100%.
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| CN112176450A (en) * | 2020-11-27 | 2021-01-05 | 嘉兴学院 | Degradable polyester fiber and preparation method thereof |
| CN112940371A (en) * | 2021-02-03 | 2021-06-11 | 建德市新莲塑化材料厂 | Method for preparing polyolefin fully-degradable master batch |
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